Organic compound destruction and removal efficiency (DRE) for plasma incinerator off-gases using an electrically heated secondary combustion chamber

The United States Department of Energy (DOE) sponsored a series pilot-scale plasma incineration tests of simulated mixed wastes at the MSE Technology Applications, Inc. technology development test facility in Butte, MT. One of the objectives of the test series was to assess the ability of an electrically heated afterburner to destroy organic compounds that may be present in the off-gases resulting from plasma incineration of mixed wastes. The anticipated benefit of an electrically heated afterburner was to decrease total off-gas volume by 50% or more, relative to fossil fuel-fired afterburners. For the present test series, feeds of interest to the DOE Mixed Waste Focus Area (MWFA) were processed in a plasma centrifugal furnace while metering selected organic compounds upstream of the electrically heated afterburner. The plasma furnace was equipped with a transferred-mode torch and was operated under oxidizing conditions (10–15% oxygen at the stack). Feeds consisted of various mixtures of soil, plastics, Portland cement, silicate fines, diesel fuel, and scrap metals. Benzene, chloroform, and 1,1,1-trichloroethane were selected for injection as simulates of organics likely to be present in DOE mixed wastes, and because of their relative rankings on the US Environmental Protection Agency (EPA) thermal stability index. The organic compounds were injected into the off-gas system at a nominal concentration of 2000 ppmv. The afterburner outlet gas stream was periodically sampled, and analyzed by gas chromatography/mass spectrometry. For the electrically heated afterburner, at operating temperatures of 1800–1980°F (982–1082°C), organic compound destruction and removal efficiencies (DREs) for benzene, chloroform, and 1,1,1-trichloroethane were found to be >99.99%. The electrically heated afterburner was also operated at temperatures well below the design operating temperature, in order to assess the sensitivity of the afterburner to temperature swings. At 1300–1320°F (704–716°C) DREs for benzene and 1,1,1-trichloroethane were still >99.99%, while the DRE for chloroform was slightly degraded to 99.977%. At 820–850°F (438–454°C) the DRE for 1,1,1-trichloroethane remained >99.99%, while the DREs for benzene and chloroform were substantially degraded, in the order expected from the EPA thermal stability index. For comparison, analogous tests were performed using a conventional natural gas fired afterburner, with similar results. The natural gas fired afterburner yielded DREs greater than 99.99% for 1,1,1-trichloroethane, chloroform, and benzene, when operated at 1600–1820°F (871–993°C) and 1350°F (732°C). Similarly to the electrically heated afterburner, at 850°F (454°C) DREs were substantially degraded for chloroform and benzene. At normal operating temperatures both the electrically heated afterburner and the natural gas fired afterburner gave acceptable DREs (>99.99%), for the three injected organic compounds. DREs remained acceptable for both units even when operated at substantially reduced temperatures.     

Laboratory scale studies on gaseous emissions generated by the incineration of an artificial automotive shredder residue presenting a critical composition

Car manufacturers must eliminate automotive shredder residues (ASR). Two ways of incineration are of interest: at 850°C in municipal waste incinerators or at higher temperatures, above 1100°C in cement plants. These processes reduce the mass and the volume of waste to be disposed of in landfills and energy recovery might be possible. Regulations govern the emission of gaseous effluents to control environmental risk. To determine gaseous effluents from a pilot sacle or an industrial incineration plant, an artificial ASR was made by mixing three representative organic polymers present in the real ASR, namely polyvinylchloride, polyurethane and rubber. This mixture was incinerated at 850 and 1100°C in laboratory experiments and the analyses of the principal gaseous effluents such as carbon oxides, nitrogen oxides, volatile organic compounds, hydrochloric and hydrocyanic acids and sulphur compounds are presented and discussed. Lastly, in order to simulate artificial ASR behaviour, the composition of the combustion gases at equilibrium was calculated using a Gibbs energy minimisation code.     

Thermal behavior characteristics of Adhesive residue

Solid wastes from organic Adhesive production are identified as toxicant hazardous wastes in China’s National Catalogue of Hazardous Wastes. The aim of this study is analyzing the thermal behavior of Adhesive residue. Its pyrolysis and combustion characteristics were investigated using thermogravimetric analysis (TGA). Experiments were carried out in the temperature range of 50–950 °C in both nitrogen and air. The results indicate that combustion under these experimental conditions largely occurs between 210 and 410 °C, whereas pyrolysis proceeds between 260 and 430 °C. Almost all weight lost takes place before 430 °C during both pyrolysis and combustion of the residue. Fourier transform infrared spectroscopy (FTIR) was used to characterize the emission characteristics during pyrolysis. When the sample is heated in an inert atmosphere, the evolution of volatiles starts around 260 °C, and reaches a peak rate at 394 °C. Most organic products evolve in a narrow temperature range during pyrolysis. The evolving gaseous products were identified as Butyraldehyde, Ether, Acetonitrile and CO₂, accompanied with some CO.     

Influence of content and particle size of waste pet bottles on concrete behavior at different w/c ratios

The goal of this work was to study the mechanical behavior of concrete with recycled Polyethylene Therephtalate (PET), varying the water/cement ratio (0.50 and 0.60), PET content (10 and 20 vol%) and the particle size. Also, the influence of the thermal degradation of PET in the concrete was studied, when the blends were exposed to different temperatures (200, 400, 600 °C). Results indicate that PET-filled concrete, when volume proportion and particle size of PET increased, showed a decrease in compressive strength, splitting tensile strength, modulus of elasticity and ultrasonic pulse velocity; however, the water absorption increased. On the other hand, the flexural strength of concrete-PET when exposed to a heat source was strongly dependent on the temperature, water/cement ratio, as well as on the PET content and particle size. Moreover, the activation energy was affected by the temperature, PET particles location on the slabs and water/cement ratio.     

Recycling of ‘waste’ FE(III)/CR(III) hydroxide for the removal of nickel from wastewater: Adsorption and equilibrium studies

Effects of Ni(II) concentration, agitation time, temperature and pH on adsorption of Ni(II) on Fe(III)/Cr(III) hydroxide, a waste by-product from fertilizer industry, have been investigated. The percent adsorption increased from 55 to 69% with increase in temperature from 20 to 40°C and from 32 to 77% with increase in pH from 3.7 to 7.5 and from 38 to 79% with decrease in Ni(II) concentration from 100 to 25 mg/L. The equilibrium data fit well with the Langmuir isotherm and the adsorption capacity was found to be 21.0 mg/g at 30°C. Thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were evaluated. The adsorption rate constant was higher at lower concentration of Ni(II) and at higher temperature. Desorption studies show that 70% of Ni(II) can be desorbed from the adsorbent at pH 4.0. The adsorbent was tested using nickel plating industry wastewater and the maximum percent removal was 97.     

Evaluation of a lime-mediated sewage sludge stabilisation process. Product characterisation and technological validation for its use in the cement industry

This paper describes an industrial process for stabilising sewage sludge (SS) with lime and evaluates the viability of the stabilised product, denominated Neutral, as a raw material for the cement industry. Lime not only stabilised the sludge, raised the temperature of the mix to 80-100 °C, furthering water evaporation, portlandite formation and the partial oxidation of the organic matter present in the sludge.Process mass and energy balances were determined. Neutral, a white powder consisting of portlandite (49.8%), calcite (16.6%), inorganic oxides (13.4%) and organic matter and moisture (20.2%), proved to be technologically apt for inclusion as a component in cement raw mixes. In this study, it was used instead of limestone in raw mixes clinkerised at 1400, 1450 and 1500 °C. These raw meals exhibited greater reactivity at high temperatures than the limestone product and their calcination at 1500 °C yielded clinker containing over 75% calcium silicates, the key phases in Portland clinker. Finally, the two types of raw meal (Neutral and limestone) were observed to exhibit similar mineralogy and crystal size and distribution.     

Solubilization and methanogenesis of a particulate industrial waste: Impact of solids loading and temperature

Effective anaerobic treatment of particulate wastes requires solubilization and acid formation prior to methanogenesis. In this case study of a particulate waste from a corn-processing industry, the influence of solids loading in solubilization, acid formation and methanogenesis was studied under mesophilic (35°C) and thermophilic (60°C) conditions. The waste was concentrated by centrifugation to initial suspended solids concentrations (TSS_i) of 150 to 350 g/L (15% to 35%). Anaerobic batch tests were conducted for 20 days, and significant solubilization of the particulate organic matter occurred in all cases. The thermophilic systems were more effective than the mesophilic systems with respect to solubilization of particulates, volatile solids destruction, acetic acid uptake, and methane generation. Methanogenesis appreared to be a rate-limiting step at higher TSS_i values, indicated by accumulation of volatile organic acids in the batch systems. Slower rates of methane production led to identification of the limiting solids loading for both temperature regimes. The results of this study can be used to evaluate the limitations of a single stage system for anaerobic treatment of organic particulate industrial wastes.     

A thermodynamic approach to the hydration of sulphate-resisting Portland cement

A thermodynamic approach is used to model changes in the hydrate assemblage and the composition of the pore solution during the hydration of calcite-free and calcite-containing sulphate-resisting Portland cement CEM I 52.5 N HTS. Modelling is based on thermodynamic data for the hydration products and calculated hydration rates for the individual clinker phases, which are used as time-dependent input parameters. Model predictions compare well with the composition of the hydrate assemblage as observed by TGA and semi-quantitative XRD and with the experimentally determined compositions of the pore solutions. The calculations show that in the presence of small amounts of calcite typically associated with Portland cement, C-S-H, portlandite, ettringite and calcium monocarbonate are the main hydration products. In the absence of calcite in the cement, however, siliceous hydrogarnet instead of calcium monocarbonate is observed to precipitate. The use of a higher water-to-cement ratio for the preparation of a calcite-containing cement paste has a minor effect on the composition of the hydrate assemblage, while it significantly changes the composition of the pore solution. In particular, lower pH value and higher Ca concentrations appear that could potentially influence the solubility and uptake of heavy metals and anions by cementitious materials.     

Remediation of petroleum-contaminated soils by fluidized thermal desorption

A novel type of fluidized bed desorber was developed for the remediation of petroleum-contaminated soils at low temperature with high efficiency. Cahn balance® was utilized to investigate the thermal desorption behavior of soils contaminated by various hydrocarbons. The performance of the fluidized-bed desorber was investigated at different operating modes. Batch operation of the fluidized-bed desorber exhibited 99.9% desorption efficiency at temperatures of ca. 300°C within a half hour. Continuous operation of the fluidized-bed indicated that Q/F (the ratio of the mass flow rate of fluidizing gas to feeding rate of contaminated soils) is less important at higher temperature (>300°C), if proper fluidization is ensured. The periodic operation of the fluidized bed desorber shows the possibility to reduce off-gas volume significantly.     

Impact of landfill liner time–temperature history on the service life of HDPE geomembranes

The observed temperatures in different landfills are used to establish a number of idealized time–temperature histories for geomembrane liners in municipal solid waste (MSW) landfills. These are then used for estimating the service life of different HDPE geomembranes. The predicted antioxidant depletion times (Stage I) are between 7 and 750 years with the large variation depending on the specific HDPE geomembrane product, exposure conditions, and most importantly, the magnitude and duration of the peak liner temperature. The higher end of the range corresponds to data from geomembranes aged in simulated landfill liner tests and a maximum liner temperature of 37 °C. The lower end of the range corresponds to a testing condition where geomembranes were immersed in a synthetic leachate and a maximum liner temperature of 60 °C. The total service life of the geomembranes was estimated to be between 20 and 3300 years depending on the time–temperature history examined. The range illustrates the important role that time–temperature history could play in terms of geomembrane service life. The need for long-term monitoring of landfill liner temperature and for geomembrane ageing studies that will provide improved data for assessing the likely long-term performance of geomembranes in MSW landfills are highlighted.     

Use of waste brick as a partial replacement of cement in mortar

The aim of this study is to investigate the use of waste brick as a partial replacement for cement in the production of cement mortar. Clinker was replaced by waste brick in different proportions (0%, 5%, 10%, 15% and 20%) by weight for cement. The physico-chemical properties of cement at anhydrous state and the hydrated state, thus the mechanical strengths (flexural and compressive strengths after 7, 28 and 90 days) for the mortar were studied. The microstructure of the mortar was investigated using scanning electron microscopy (SEM), the mineralogical composition (mineral phases) of the artificial pozzolan was investigated by the X-ray diffraction (XRD) and the particle size distributions was obtained from laser granulometry (LG) of cements powders used in this study. The results obtained show that the addition of artificial pozzolan improves the grinding time and setting times of the cement, thus the mechanical characteristics of mortar. A substitution of cement by 10% of waste brick increased mechanical strengths of mortar. The results of the investigation confirmed the potential use of this waste material to produce pozzolanic cement.     

The effect of supercritical carbon dioxide treatment on the leachability and structure of cemented radioactive waste-forms

The former process for the cementation of transuranic (TRU) low-level wastes poses several technical problems. Specifically in the US a TRU waste-form has not yet passed the Waste Isolation Pilot Plant prohibition for free liquid. For this reason, treatment of the portland cement based waste-form with supercritical carbon dioxide (SCCO₂) is shown to satisfy regulations. The effect of SCCO₂ treatment by applying different CO₂ pressure and temperature conditions (8.4 MPa<p<28 MPa, 35°C<T<62°C) on the leachability, phase constitution, and microstructure of surrogate-doped portland cement type I/II samples is presented. Leaching studies were performed using a synthetic groundwater leaching procedure. Changes in phase constitution of the major crystalline phases (Ca(OH)₂, CaCO₃) as well as the microstructure were measured by X-ray diffraction and scanning electron microscopy. SCCO₂ treatment at 8.4 MPa and 35°C can be shown as the most promising conditions to satisfy the requirements of the Department of Transportation (DOT) and to enhance the natural aging reaction of cement paste by carbonation, combined with the lowest release rates of the surrogates ²³²Th, and ^151/153Eu.     

Recovery of metal values from zinc solder dross

Zinc solder dross containing 14.8% Sn, 16.3% Pb, 0.41% Al and 64.5% Zn was leached with 3% H₂SO₄ at 45°C for 1 h. Zinc and aluminum went into solution, whereas lead and tin remained with the residue. Aluminum was selectively precipitated as calcium aluminum carbonate by treating the sulphate leachate with limestone at pH 4.8. Zinc sulphate solution was either evaporated to obtain zinc sulphate crystals or precipitated as basic zinc carbonate at pH 6.8. The undissolved lead and tin were leached with 5 M hot hydrochloric acid. The major part of lead chloride ( 73%) was separated by cooling the leached products down to room temperature. From the soluble fraction, tin was recovered as hydrated tin oxide by alkylation with caustic soda at pH 2.4, while the remaining lead was separated at pH 8.5 as lead hydroxide. A process flowsheet had been suggested which involved two-stage hydrometallurgical treatment. Parameters affecting the recovery efficiency of the suggested method such as temperature, time, pH and acid: solid stoichiometric ratio were investigated. Results obtained revealed that the optimum leaching conditions were achieved by using 20 ml of 3% H₂SO₄ acid/g dross for 1 h at 45°C. Recovery efficiency of the metal salts was 99.1, 99.4, 99.6 and 99.5% for Zn, Al, Pb and Sn respectively. Recovery efficiency was related to the solubility of the concerned salts under the given experimental conditions.     

Effects of recycled glass substitution on the physical and mechanical properties of clay bricks

In this study, wasted glasses from structural glass walls up to 45 wt.% were added into clay mixtures in brick manufacturing process. Physical and mechanical properties of clay bricks were investigated as functions of the wasted glass content and the firing temperature. The results indicated that with proper amount of wasted glasses and firing temperature, clay bricks with suitable physical and mechanical properties could be obtained. The compressive strength as high as 26–41 MPa and water absorption as low as 2–3% were achieved for bricks containing 15–30 wt.% of glass content and fired at 1100 °C. When the glass waste content was 45 wt.%, apparent porosity and water absorption was rapidly increased.     

High fire resistance in blocks containing coal combustion fly ashes and bottom ash

Fire resistance recycled blocks, containing fly ash and bottom ash from coal combustion power plants with a high fire resistance, are studied in this paper by testing different compositions using Portland cement type II, sand, coarse aggregate and fly ash (up to 50% of total weight) and bottom ash (up to 30% of total weight). The fire resistance, physical-chemical (density, pH, humidity, and water absorption capacity), mechanical (compressive and flexural strength), and leaching properties are measured on blocks made with different proportions of fly ash and bottom ash. The standard fire resistance test is reproduced on 28 cm-high, 18 cm-wide and 3 cm-thick units, and is measured as the time needed to reach a temperature of 180 °C on the non-exposed surface of the blocks for the different compositions.The results show that the replacement of fine aggregate with fly ash and of coarse aggregate with bottom ash have a remarkable influence on fire resistance and cause no detriment to the mechanical properties of the product. Additionally, according to the leaching tests, no environmental problems have been detected in the product. These results lead to an analysis of the recycling possibilities of these by-products in useful construction applications for the passive protection against fire.     

Cost-effective approach to ethanol production and optimization by response surface methodology

Food wastes disposed from residential and industrial kitchens have gained attention as a substrate in microbial fermentations to reduce product costs. In this study, the potential of simultaneously hydrolyzing and subsequently fermenting the mixed carbohydrate components of kitchen wastes were assessed and the effects of solid load, inoculum volume of baker’s yeast, and fermentation time on ethanol production were evaluated by response surface methodology (RSM). The enzymatic hydrolysis process was complete within 6 h. Fermentation experiments were conducted at pH 4.5, a temperature of 30 °C, and agitated at 150 rpm without adding the traditional fermentation nutrients. The statistical analysis of the model developed by RSM suggested that linear effects of solid load, inoculum volume, and fermentation time and the quadratic effects of inoculum volume and fermentation time were significant (P < 0.05). The verification experiments indicated that the developed model could be successfully used to predict ethanol concentration at >90% accuracy. An optimum ethanol concentration of 32.2 g/l giving a yield of 0.40 g/g, comparable to yields reported to date, was suggested by the model with 20% solid load, 8.9% inoculum volume, and 58.8 h of fermentation. The results indicated that the production costs can be lowered to a large extent by using kitchen wastes having multiple carbohydrate components and eliminating the use of traditional fermentation nutrients from the recipe.     

Study of Aging Characteristics of Ternary Blends of Polyethylenes—II

Six film samples of low-density polypropylene (LDPE)/linear LDPE (LLDPE)/high-density polypropylene (HDPE) with varying ratios of LDPE (20–45 ... wt%) and LLDPE (25–50 wt%) having a fixed amount of HDPE at 30 wt% were prepared by blown film extrusion technique. The samples were aged at four different temperatures, 55°, 70°, 85°, and 100°C, for four different time periods in the interval of between 150 hours and up to 600 hours. The change in the structure of various constituents and the formation of various oxygenated (peroxy and hydroperoxy) and unsaturated groups during thermo-oxidative degradation was discussed by infrared spectroscopy. The visiosity-average molecular weight was found to have decreased slowly in the initial aging hours and temperatures, whereas it decreased by 10% with its previous value tensile strength that is, 100°C when aged for 600 hours. The tensile strength of the sample first increased by 67% at 55°C and 89% at 70°C up to 450 hours, whereas the values increased by 52.5% at 85°C and 33.9% at 100°C when aged for 150 hours and then decreased. The percentage elongation at break increased by 2.7% at 55°C and 10.7% at 70°C for 150 and 300 hours of aging, respectively, whereas the percentage decreased when aged at 85°C and 100°C for up to 600 hours of aging. The values of gel content (percent) increased and initial degradation temperature decreased with aging time and temperature.     

Laboratory stabilization/solidification of surrogate and actual mixed-waste sludge in glass and grout

Grout and glass formulations were developed for the stabilization of highly radioactive tank sludges. These formulations were tested in the laboratory with a surrogate and with a sample of an actual mixed waste tank sludge. The grout formulation was tested at wet-sludge loadings of 50–60 wt%, giving a volume increase of about 40–50 vol%. Dried sludge was vitrified into glass at waste oxide loadings of 40–50 wt%, giving a volume decrease of about 50–60 vol%. The Resource Conservation and Recovery Act (RCRA) metals included in surrogate testing were Ag, Ba, Cd, Cr, Ni, Pb, Se, Tl and Hg. Since vitrification would volatilize, not stabilize mercury, it was not included in the surrogates vitrified. The actual sludge sample was only characteristically hazardous for mercury by the toxic characteristic leaching procedure (TCLP) but exceeded the Universal Treatment Standard (UTS) limit for chromium. The grout and glass formulations stabilized these RCRA metals within UTS limits. In addition, a grout leachability index of about 9–10 was measured for both ⁸⁵Sr and ¹³⁷Cs, meeting the recommended requirement of >6. The glass leachability index was estimated to be >18 for cold cesium and strontium.     

Sorption of strontium on bentonite

Sorption of Sr on bentonite was studied using the batch technique. Distribution coefficients (K_d) were determined as a function of contact time, pH, sorbent and sorbate concentration and temperature. The data were interpreted in terms of Freundlich, Langmuir and Dubinin-Radushkevich isotherms. Thermodynamic parameters for the sorption system were determined at three different temperatures. The positive value of the heat of sorption, ΔH° = 30.62 kJ/mol at 298 K, shows that the sorption of strontium on bentonite is endothermic. The negative value of the free energy of sorption, ΔG° = −10.69 kJ/mol at 298 K, shows the spontaneity of the reaction. ΔG° becomes more negative with increasing temperature, which shows that the sorption process is more favorable at higher temperatures. The mean free energy for sorption, E 9 kJ/mol, suggests that ion exchange is the predominant mode of sorption in the Sr concentration range studied, i.e. 0.01 – 0.3 mol/dm³. The presence of complementary cations depresses the sorption of strontium on bentonite in the order Ca²⁺>Mg²⁺>K⁺>Na⁺. Some organic complexing agents and natural ligands also affect the sorption of strontium. The desorption studies with ground water at low strontium loadings on bentonite show that about 90% of Sr is irreversibly sorbed on the bentonite.     

Immobilisation of heavy metal in cement-based solidification/stabilisation: a review

Heavy metal-bearing waste usually needs solidification/stabilization (s/s) prior to landfill to lower the leaching rate. Cement is the most adaptable binder currently available for the immobilisation of heavy metals. The selection of cements and operating parameters depends upon an understanding of chemistry of the system. This paper discusses interactions of heavy metals and cement phases in the solidification/stabilisation process. It provides a clarification of heavy metal effects on cement hydration. According to the decomposition rate of minerals, heavy metals accelerate the hydration of tricalcium silicate (C3S) and Portland cement, although they retard the precipitation of portlandite due to the reduction of pH resulted from hydrolyses of heavy metal ions. The chemical mechanism relevant to the accelerating effect of heavy metals is considered to be H+ attacks on cement phases and the precipitation of calcium heavy metal double hydroxides, which consumes calcium ions and then promotes the decomposition of C3S. In this work, molecular models of calcium silicate hydrate gel are presented based on the examination of 29Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). This paper also reviews immobilisation mechanisms of heavy metals in hydrated cement matrices, focusing on the sorption, precipitation and chemical incorporation of cement hydration products. It is concluded that further research on the phase development during cement hydration in the presence of heavy metals and thermodynamic modelling is needed to improve effectiveness of cement-based s/s and extend this waste management technique.